Brazilian Oil Spills Chemical Characterization—Case Studies

In the last decade, PETROBRAS has experienced some significant oil spills cases and the PETROBRAS Research Center has played an important role in the company emergency response program by characterizing the spilled oil, monitoring the affected ecosystem, determining the fate of the oil in the environment, and, subsequently, helping the company in assessing the environmental damage. This paper presents the use of advanced chemical analytical techniques (GC/FID, P&T/GC/PID and GC/MS) in some Brazilian oil spill studies in order to determine fractions and individual petroleum hydrocarbons in different matrices such as water, groundwater, sediment, sand, fish and the spilled oil itself. The spill studies encompassed crude and fuel oil releases on land and coastal ecosystems, related to the incidents in Guanabara Bay (Rio de Janeiro), Barigui and Iguassu Rivers (Parana) and Sao Sebastiao Channel (Sao Paulo). Total petroleum hydrocarbons (TPH), n -alkanes, isoprenoids, unresolved complex mixtures (UCM), volatile monoaromatic compounds—benzene, toluene, ethylbenzene and xylenes (BTEX), parent and alkylated homologues polycyclic aromatic hydrocarbons (PAH), and terpanes and steranes were characterized for determining correlation to the spilled oil and other known oil sources and environmental assessment. Some of the acute ecotoxicity data for water and sediment samples is also presented.     

GC × GC--A New Analytical Tool For Environmental Forensics

Comprehensive two-dimensional gas chromatography, GC 2 GC, is a new analytical tool with a tremendous capability to separate and identify organic compounds in complex environmental samples. GC 2 GC uses two different chromatography columns coupled serially by a modulator to produce a volatility by polarity separation and distribute compound peaks across a two-dimensional retention time plane. The two-dimensional separation produces an order of magnitude more resolved peaks than traditional GC methods. The grouping or ordering of the peaks in the GC 2 GC chromatogram facilitates the identification of unknown compounds and the comparison of complex environmental samples. When a mass spectrometer detector is used, each resolved GC 2 GC peak yields a single-component, interference-free mass spectrum that leads to accurate matching with mass spectral libraries. GC 2 GC examination of marine sediment extracts identified a wide variety of chemical contaminants including polychlorinated biphenyls, p -nonylphenol isomers, polycyclic aromatic hydrocarbons, benzotriazoles, and the alkane, cycloalkane, alkylbenzene, alkylnaphthalene, and biomarker fractions of petroleum. The two-dimensional GC 2 GC chromatogram image permits rapid screening of the sediment extracts for these and other unknown contaminants.     

A Strategy and Methodology for Defensibly Correlating Spilled Oil to Source Candidates

The source of crude oils and petroleum products released into navigable waterways and shipping lanes is not always known. Thus, the defensible identification of spilled crude oils and petroleum products and their correlation to suspected sources is a critical part of many oil spill assessments. Quantitative "fingerprinting" analysis, when evaluated using straightforward statistical and numerical analyses, provides a defensible means to differentiate among qualitatively similar oils and provides the best assessment of the source(s) for spilled oils. Polycyclic aromatic hydrocarbon (PAH) and petroleum biomarker concentration data are a particularly useful quantitative measure that can benefit most oil spill investigations. In this paper the strategy and methodology for correlation analysis that relies upon quantitative gas chromatography/mass spectrometry operated in the selected ion monitoring mode (GC/MS-SIM) is demonstrated in a case study involving 66 candidate sources for a heavy fuel oil spill of unknown origin. The strategy includes identification of 19 chemical indices (out of 45 evaluated) based upon PAH's and biomarkers that were (1) independent of weathering; and (2) precisely measured, both of which are determined by statistical analysis of the data. The 19 chemical indices meeting these criteria are subsequently analysed using principal component analysis (PCA), which helps to determine defensibly the "prime suspects" for the oil spill under investigation. The strategy and methodology described, which combines statistical and numerical analysis of quantitative chemical data, can be adapted and applied to other environmental forensic investigations with the objective of correlating any form of contamination to its suspected sources.     

A Strategy and Methodology for Defensibly Correlating Spilled Oil to Source Candidates

The source of crude oils and petroleum products released into navigable waterways and shipping lanes is not always known. Thus, the defensible identification of spilled crude oils and petroleum products and their correlation to suspected sources is a critical part of many oil spill assessments. Quantitative “fingerprinting” analysis, when evaluated using straightforward statistical and numerical analyses, provides a defensible means to differentiate among qualitatively similar oils and provides the best assessment of the source(s) for spilled oils. Polycyclic aromatic hydrocarbon (PAH) and petroleum biomarker concentration data are a particularly useful quantitative measure that can benefit most oil spill investigations. In this paper the strategy and methodology for correlation analysis that relies upon quantitative gas chromatography/mass spectrometry operated in the selected ion monitoring mode (GC/MS-SIM) is demonstrated in a case study involving 66 candidate sources for a heavy fuel oil spill of unknown origin. The strategy includes identification of 19 chemical indices (out of 45 evaluated) based upon PAH's and biomarkers that were (1) independent of weathering; and (2) precisely measured, both of which are determined by statistical analysis of the data. The 19 chemical indices meeting these criteria are subsequently analysed using principal component analysis (PCA), which helps to determine defensibly the “prime suspects” for the oil spill under investigation. The strategy and methodology described, which combines statistical and numerical analysis of quantitative chemical data, can be adapted and applied to other environmental forensic investigations with the objective of correlating any form of contamination to its suspected sources.     

Soil Gas Methane at Petroleum Contaminated Sites: Forensic Determination of Origin and Source

Hydrocarbon vapors associated with spilled petroleum products arouse regulatory concern and can pose a significant health and safety risk. While petroleum products do not contain a significant amount of methane (CH 4 ), high CH 4 contents in soil gas near petroleum spills have been reported. While CH 4 is nontoxic, its accumulation in shallow soil gas represents a potential explosion and asphyxiation hazard, especially in confined spaces. Identifying the source and origin of shallow CH 4 accumulations is an important part of evaluating potential exposure pathways, selecting appropriate remedial measures, and determining environmental liability. This paper discusses the potential nature and anthropogenic sources for shallow CH 4 and how integration of geological, geochemical, and land use data can be used to determine its origin and identify its source. Two case studies are presented, one where CH 4 associated with a gasoline spill is shown to be derived from a natural source rather than the gasoline, and a second where CH 4 associated with spilled crude oil is shown to be produced in the vadose zone by biodegradation of the oil.     

Soil Gas Methane at Petroleum Contaminated Sites: Forensic Determination of Origin and Source

Hydrocarbon vapors associated with spilled petroleum products arouse regulatory concern and can pose a significant health and safety risk. While petroleum products do not contain a significant amount of methane (CH₄), high CH₄contents in soil gas near petroleum spills have been reported. While CH₄is nontoxic, its accumulation in shallow soil gas represents a potential explosion and asphyxiation hazard, especially in confined spaces. Identifying the source and origin of shallow CH₄accumulations is an important part of evaluating potential exposure pathways, selecting appropriate remedial measures, and determining environmental liability. This paper discusses the potential nature and anthropogenic sources for shallow CH₄and how integration of geological, geochemical, and land use data can be used to determine its origin and identify its source. Two case studies are presented, one where CH₄associated with a gasoline spill is shown to be derived from a natural source rather than the gasoline, and a second where CH₄associated with spilled crude oil is shown to be produced in the vadose zone by biodegradation of the oil.     

Potential of the microbial community present in an unimpacted beach sediment to remediate petroleum hydrocarbons

The potential of the microbial communities present in the intertidal zone of an unimpacted beach (a beach that did not suffer any significant oil spill) to degrade hydrocarbons was investigated. For that, laboratory-based microcosms (50-ml flasks) were set up with sandy beach sediment spiked with crude oil and incubated with local seawater for 15 days in the dark. Three bioremediation treatments were tested (biostimulation (BS), autochthonous bioaugmentation (AB), and combined treatment of biostimulation + bioaugmentation (BS + AB)) and the results were compared with natural attenuation (NA). Visual inspection showed clearly an oil solubility increase (confirmed by a higher hydrocarbons concentration in supernatant solutions) for all tested treatments when compared to NA. Significant degradation of the oil, shown by different profiles of petroleum hydrocarbons, was also observed for the different treatments particularly for BS + AB. Therefore, the microbial community of this unimpacted beach sediment could respond to an oil spill, degrading hydrocarbons. But to increase the natural attenuation pace, obtained results indicated that BS + AB is an appropriate approach for the bioremediation of beaches recently impacted by an oil spill. The autochthonous microbial cultures can be obtained “before” or “after” the contamination of the target site, being inoculated into the site right after it contamination.     

Development and verification of a screening model for surface spreading of petroleum

Overflows and leakage from aboveground storage tanks and pipelines carrying crude oil and petroleum products occur frequently. The spilled hydrocarbons pose environmental threats by contaminating the surrounding soil and the underlying ground water. Predicting the fate and transport of these chemicals is required for environmental risk assessment and for remedial measure design. The present paper discusses the formulation and application of the Oil Surface Flow Screening Model (OILSFSM) for predicting the surface flow of oil by taking into account infiltration and evaporation. Surface flow is simulated using a semi-analytical model based on the lubrication theory approximation of viscous flow. Infiltration is simulated using a version of the Green and Ampt infiltration model, which is modified to account for oil properties. Evaporation of volatile compounds is simulated using a compositional model that accounts for the changes in the fraction of each compound in the spilled oil. The coupling between surface flow, infiltration and evaporation is achieved by incorporating the infiltration and evaporation fluxes into the global continuity equation of the spilled oil. The model was verified against numerical models for infiltration and analytical models for surface flow. The verification study demonstrates the applicability of the model.     

Assessment of crude oil biodegradation in arctic seashore sediments: effects of temperature,salinity, and crude oil concentration

The expected increase in offshore oil exploration and production in the Arctic may lead to crude oil spills along arctic shorelines. To evaluate the potential effectiveness of bioremediation to treat such spills, oil spill bioremediation in arctic sediments was simulated in laboratory microcosms containing beach sediments from Barrow (Alaska), spiked with North Slope Crude, and incubated at varying temperatures and salinities. Biodegradation was measured via respiration rates (CO₂ production); volatilization was quantified by gas chromatography/mass spectrophotometry (GC/MS) analysis of hydrocarbons sorbed to activated carbon, and hydrocarbons remaining in the sediment were quantified by GC/flame ionization detector (FID). Higher temperature leads to increased biodegradation by naturally occurring microorganisms, while the release of volatile organic compounds was similar at both temperatures. Increased salinity had a small positive impact on crude oil removal. At higher crude oil dosages, volatilization increased, however CO₂ production did not. While only a small percentage of crude oil was completely biodegraded, a larger percentage was volatilized within 6–9 weeks.     

Simulation of interactions between migrating whales and potential oil spills

A numerical model system was developed to quantify the probability of endangered bowhead and gray whales encountering spilled oil in Alaskan waters. Migration and diving-surfacing models for bowhead and gray whales, and an oil spill trajectory model comprise the system. The migration models were developed from conceptual considerations, then calibrated with and tested against observations. The distribution of whales is represented in space and time by discrete points, each of which may represent one or more whales. The movement of a whale point is governed by a random walk algorithm which stochastically follows a migratory pathway. Stochastic diving-surfacing models are used to stimulate surfacing behavior sequences for each species. The oil spill model accounts for oil transport and spreading in open water and in the presence of sea ice. Historical wind records and ice cover data sets provide the environmental conditions to generate stochastic oil spill scenarios. The oil spill, whale migration and diving-surfacing models are linked to provide quantitative estimates of whale-oil interactions. The model system was applied to the Alaskan Beaufort Sea to investigate the probability that bowhead whales would encounter oil spilled in this region.     

Impact of climate change and seasonal trends on the fate of Arctic oil spills

We investigated the effects of a warmer climate, and seasonal trends, on the fate of oil spilled in the Arctic. Three well blowout scenarios, two shipping accidents and a pipeline rupture were considered. We used ensembles of numerical simulations, using the OSCAR oil spill model, with environmental data for the periods 2009–2012 and 2050–2053 (representing a warmer future) as inputs to the model. Future atmospheric forcing was based on the IPCC’s A1B scenario, with the ocean data generated by the hydrodynamic model SINMOD. We found differences in “typical” outcome of a spill in a warmer future compared to the present, mainly due to a longer season of open water. We have demonstrated that ice cover is extremely important for predicting the fate of an Arctic oil spill, and find that oil spills in a warming climate will in some cases result in greater areal coverage and shoreline exposure.     

Petroleum Pollutant Degradation by Surface Water Microorganisms (8 pp)

Background, Aims and Scope It is well known that the composition of petroleum or some of its processing products changes in the environment mostly under the influence of microorganisms. A series of experiments was conducted in order to define the optimum conditions for an efficient biodegradation of petroleum pollutant, or bioremediation of different segments of the environment. The aim of these investigations was to show to what extent the hydrocarbons of a petroleum pollutant are degraded by microbial cultures which were isolated as dominant microorganisms from a surface water of a wastewater canal of an oil refinery and a nitrogen plant. Biodegradation experiments were conducted on one paraffinic, and one naphthenic type of petroleum during a three month period under aerobic conditions, varying the following parameters: Inorganic (Kp) or an organic medium (Bh) with or without exposition to light. Methods Microorganisms were analyzed in a surface water sample from a canal (Pančevo, Serbia), into which wastewater from an oil refinery and a nitrogen plant is released. The consortia of microorganisms were isolated from the water sample (most abundant species: Phormidium foveolarum - filamentous Cyanobacteria, blue-green algae and Achanthes minutissima, diatoms, algae). The simulation experiments of biodegradation were conducted with the biomass suspension and crude oils Sirakovo (Sir, paraffinic type) and Velebit (Ve, naphthenic type). After a three month period, organic substance was extracted by means of chloroform. In the extracts, the content of saturated hydrocarbons, aromatic hydrocarbons, alcohols and fatty acids was determined (the group composition). n-Alkanes and isoprenoid aliphatic alkanes, pristane and phytane, in the aliphatic fractions, were analyzed using gas chromatography (GC). Total isoprenoid aliphatic alkanes and polycyclic alkanes of sterane and triterpane types were analyzed by GC-MS. Results and discussion. Paraffinic type petroleums have a significant loss of saturated hydrocarbons. For naphthenic type petroleum, such a trend has not been observed. The most intensive degradation of n-alkanes and isoprenoid aliphatic alkanes (in paraffinic oil) and isoprenoids (in naphthenic oil) was observed using the inorganic medium Kp in the light; the microbial conversion is somewhat lower with Kp in the dark; with organic medium Bh in the light the degradation is of low intensity; with the same medium in the dark the degradation is hardly to be seen. Steranes and triterpanes were not affected by microbial degradation under the conditions used in our experiments. Obviously, the petroleum biodegradation was restricted to the acyclic aliphatics (n-alkanes and isoprenoids). Conclusion Phormidium foveolarum (filamentous Cyanobacteria - blue-green algae) and Achanthes minutissima (diatoms, algae), microbial cultures isolated as dominant algae from a surface water in a wastewater canal of an oil refinery and a nitrogen plant, have degradable effects dominantly involving petroleum hydocarbons. Petroleum microbiological degradation is more intensive when inorganic medium (in the light) is applied. Having in mind that the inorganic pollutants have been released into the canal as well, this medium reflects more the natural environmental conditions. Polycyclic alkanes of sterane and triterpane type, in spite of the fact that these compounds could be degraded, have remained unchanged regarding abundance and distribution. Since this is the case even for naphthenic type petroleum (which is depleted in n-alkanes), it can be concluded that the biodegradation of petroleum type pollutants, under natural conditions, will be restrained to the n-alkane and isoprenoid degradation. Recommendation and Outlook Performed experiments and simulations of petroleum microbiological degradation may serve for the prediction of the fate of petroleum type pollutants, as well as for definition of conditions for bioremediation of some environmental segments.     

GC and GC-MS characterization of crude oil transformation in sediments and microbial mat samples after the 1991 oil spill in the Saudi Arabian Gulf coast

The massive oil discharge in the Saudi Arabian coast at the end of the 1991 Gulf War is used here as a natural experiment to study the ability of microbial mats to transform oil residues after major spills. The degree of oil transformation has been evaluated from the analysis of the aliphatic and aromatic hydrocarbons by gas chromatography (GC) and GC coupled to mass spectrometry (GC-MS). The oil-polluted microbial mat samples from coastal environments exhibited an intermediate degree of transformation between that observed in superficial and deep sediments. Evaporation, photo-oxidation and water-washing seemed to lead to more effective and rapid elimination of hydrocarbons than cyanobacteria and its associated microorganisms. Furthermore, comparison of some compounds (e.g. regular isoprenoid hydrocarbons or alkylnaphthalenes) in the oil collected in the area after the spill or in the mixtures retained by cyanobacterial growth gave rise to an apparent effect of hydrocarbon preservation in the microbial mat ecosystems.     

A Holistic Approach to Hydrocarbon Source Allocation in the Subtidal Sediments of Prince William Sound,Alaska, Embayments

Prince William Sound (PWS), Alaska has an extensive history of human and industrial activity that has produced a complex organic geochemistry record in subtidal sediments of embayments throughout the sound. In addition to contributions from recent oil spills and a regional background of natural petroleum hydrocarbons originating from active hydrocarbon systems in the northern Gulf of Alaska (GOA), pyrogenic and petrogenic PAH were, and continue to be introduced to subtidal sediments at numerous sites of past and present human activities. These sites include villages, fish hatcheries, fish camps and recreational campsites in addition to abandoned settlements, canneries, sawmills, and mines. A holistic approach is used to fingerprint and quantify hydrocarbon contributions from multiple sources in a sediment sample. It involves acquiring a comprehensive understanding of the history of the area to identify potential sources, collection of representative samples, and accurate quantitative analyses of the source and sediment samples for a suite of diagnostic PAH analytes and chemical biomarker compounds. Unlike the deepwater sediments of the sound and GOA, the TOC tool, described elsewhere, does not work as well in some restricted embayments due to their high contents of recent organic matter (ROM). The current study employs a constrained least-squares algorithm to allocate hydrocarbon sources contributing to subtidal sediments collected from PWS embayments in 1991, 1999 and 2000. Results show that sources contributing to the natural petrogenic background are present in the embayments, pyrogenic hydrocarbons including combustion products of diesel are important where human activity was high, and petroleum produced from the Monterey Formation (CA) is present locally. Oil and asphalt shipped from California were widely used for fuel and construction prior to development of the Cook Inlet and North Slope fields. In certain locations that were oiled in 1989, low levels of highly degraded Alaska North Slope crude oil residues attributable to the Exxon Valdez spill remain.     

Toxicity of crude oil to the mayfly, Hexagenia bilineata (Ephemeroptera: Ephemeridae)

Effects of crude oil on survival and behavior of the mayfly Hexagenia bilineata were evaluated in laboratory studies. Mayfly nymphs were exposed to the water soluble and oil residue fractions of crude oil. Mayfly survival was not reduced by a 96-h exposure to either the water soluble fraction or the oil residue mixed with sediment. However, significant mortality did result from a 21-day exposure to oil residue mixed with sediment at concentrations as low as 500 microg g(-1). Survival was also reduced after a 21-day exposure to oil-contaminated sediments (1905 microg g(-1)) collected 6 weeks after a crude oil spill in the Chariton River, Missouri. In a behavioral test measuring habitat exclusion, organisms did not avoid contact with sediment containing oil residue (50-800 microg g(-1)). Collectively, results from these studies indicate that exposure to oil residue in sediment will reduce survival of H. bilineata in the laboratory and may reduce survival in the environment for 6 weeks or more after an oil spill.     

A Holistic Approach to Hydrocarbon Source Allocation in the Subtidal Sediments of Prince William Sound,Alaska, Embayments

Prince William Sound (PWS), Alaska has an extensive history of human and industrial activity that has produced a complex organic geochemistry record in subtidal sediments of embayments throughout the sound. In addition to contributions from recent oil spills and a regional background of natural petroleum hydrocarbons originating from active hydrocarbon systems in the northern Gulf of Alaska (GOA), pyrogenic and petrogenic PAH were, and continue to be introduced to subtidal sediments at numerous sites of past and present human activities. These sites include villages, fish hatcheries, fish camps and recreational campsites in addition to abandoned settlements, canneries, sawmills, and mines. A holistic approach is used to fingerprint and quantify hydrocarbon contributions from multiple sources in a sediment sample. It involves acquiring a comprehensive understanding of the history of the area to identify potential sources, collection of representative samples, and accurate quantitative analyses of the source and sediment samples for a suite of diagnostic PAH analytes and chemical biomarker compounds. Unlike the deepwater sediments of the sound and GOA, the TOC tool, described elsewhere, does not work as well in some restricted embayments due to their high contents of recent organic matter (ROM). The current study employs a constrained least-squares algorithm to allocate hydrocarbon sources contributing to subtidal sediments collected from PWS embayments in 1991, 1999 and 2000. Results show that sources contributing to the natural petrogenic background are present in the embayments, pyrogenic hydrocarbons including combustion products of diesel are important where human activity was high, and petroleum produced from the Monterey Formation (CA) is present locally. Oil and asphalt shipped from California were widely used for fuel and construction prior to development of the Cook Inlet and North Slope fields. In certain locations that were oiled in 1989, low levels of highly degraded Alaska North Slope crude oil residues attributable to the Exxon Valdez spill remain.     

Environmental photooxidation of dibenzothiophenes following the Amoco Cadiz oil spill

Photooxidation products of dibenzothiophenes (sulfur containing petroleum heteroaromatic hydrocarbons) were characterized in an oil slick sample obtained from a field location following the AMOCO CADIZ oil spill. The same oxidation products were formed in the laboratory by the photooxidation of a medium Arabian crude oil which contained the identical precursor hydrocarbons. Analytical techniques included fractionation by liquid/solid chromatography and characterization using high resolution gas chromatography-mass spectrometry. To the best of the author's knowledge, this represents the first reported instance for the formation of photooxidation products following an actual oil spill. A comparison of the quantities of various oxidation products was carried out by quantitative mass spectrometry using extracted ion current profiles of dibenzothiophenes and their corresponding sulfoxides. The geochemical and physiological implications of such photooxidation processes are also discussed.     

Source Apportionment and Identification of Polycyclic Aromatic Hydrocarbons (PAHs) in Sediment Cores of Selected Creeks in Delta State,Nigeria

Polycyclic aromatic hydrocarbons (PAHs) seasonal variation and sources in Ubeji, Ifie, and Egbokodo Creeks of the Niger Delta, Nigeria, were predicted using diagnostic ratios (DRs) of parent PAHs (Phe/Phe + Ant; Flu/Flu + Pyr; BaA/BaA + Chry, and Ind/Ind + BghiP) and principal component analysis (PCA). A total of 222 sediment core samples were collected during the wet (August 2010) and the dry seasons (January 2011). The samples were dried and Soxhlet extracted; sample extracts were fractionated and analyzed by gas chromatography/flame ionization detection (GC/FID) to identify individual PAHs. The diagnostic PAH ratios revealed that PAHs in the sediment cores at the three creeks, in both seasons, mainly stemmed from the combustion process (pyrogenic sources). Principal component analysis further confirmed that wood-burning, coal combustion, diesel, gasoline-powered vehicular emissions, and petroleum combustion were the dominant contributors of PAHs sources at the sampling location. This study provided information on the origin and sources of PAHs in sediment cores, which may be useful for regulatory actions, environmental quality management, contamination history, and environmental forensic studies.     

The toxicity and concentrations of PAHs in creosote-contaminated lake sediment

Sediment samples, divided into three layers (0-10, 10-20 and 20-30 cm), were collected from 16 sites in Lake J?ms?nvesi, Central Finland. The acute toxicity of pore waters and elutriates (sediment + water 1:4 v/v) were studied by bioluminescence inhibition test and by immobilisation of water fleas (Daphnia magna Straus). Concentrations of polycyclic aromatic hydrocarbons (PAHs) in sediments and elutriates were measured by gas chromatography using flame ionization detection (GC/FID). The highest total PAH concentration was 3.3 mg/g dry weight in the sediment and up to 1.7 mg/l in the elutriate of the uppermost (0-10 cm) layer, also being the most toxic to photoluminencent bacteria and water flea. When sediment and water mix, like during dredging operations, toxic compounds may spread from the sediment to the water column and can pose on environmental risk.     

Evaluation of zoobenthic assemblages and recovery following petroleum spill in a coastal area of Río de la Plata estuarine system, South America

The objective of this work was to analyse zoobenthic assemblages in the coastal sector of the Río de La Plata, Argentina, after a petroleum spill. Sampling stations were located in representative sites of various landscapes. Structure, composition, physico-chemical parameters and seasonal changes were recorded in order to assess taxocenosis evolution during the period 1999–2003. Recovery signs were estimated by means of biotic indices and the presence of sensitive species. Tolerant species were dominant in heavily polluted sites, with low diversity and water quality values, according to the biotic indices used. In certain zones, sediment quality remains impoverished, with a visible oil film on the surface. However, during the last sampling, some points showed an increase in biotic indices, pointing to a slight improvement in environmental conditions.